Synthetic compositions



Patented June 12, 1945 SYNTHETIC COMPOSITIONS Gaetano F. DAlelio,Pittsfleld, Mass aasignor to General Electric Company, a corporation ofNew York No Drawing. Application February 5, 1941, Serial No. 371,524

31 Claims. I ('01. 260-39) This invention relates to the production ofnew and usei'ul synthetic compositions. More particu .ureas, methyloimelamines, etc., and an amino acid or a salt thereof or a mixture of anamino acid and a salt thereof. The aminotriazines (includingiminotriazines) and the amino acids and salts thereof (including iminoacids and salts thereof) used in carrying the present invention intoeffect have at least one hydrogen atom attached to an amino nitrogenand, therefore, can be caused to r act with an activemethylenecontainingbody.

This application i a continuation-in-part of my copending applicationSerial No. 256,998, filed February 17, 1939, and Serial No. 363,035,filed October 26, 1940, both of which applications are assigned to thesame assignee'as the present invention. In application Serial No.256,998 I described the preparation of new reaction products of a monoorpoly-amide,-an aldehyde and an aldehyde-reactable organic amphotericsubstance free from polypeptide linkages, for example amino acids suchas glycine, heterogeneous amino acids such as sulfamic acid andbeta-aminoethyl suli'onic acid. etc. In copending application Serial No.363,035 I disclosed and claimed aminoplasts modified with a specificamino acid, namely, sulfamic acid-more specific examples of suchmodifled aminoplasts being condensation products of a. mixturecomprising formaldehyde, sulfamic acid and an aminotriazine or both aurea and an minotriazine.

The amino acids used in carrying the present invention into efie ct areamphoteric substances and are not to be confused with th proteids andpartially hydrolyzed proteids, examples of which are glycinin, zein,casein, legumin, gliadin and phaseolin, merely to mention a few. Theseproteid compounds are non-crystalloidal, water-insoluble bodies havingpolypeptide linkages and the coll idal properties of the high molecularweight proteins, as exemplified by viscosity and osmotic pressurephenomena. When the proteids or their alkali salts are -plasticized, forexample with water, alcohol, etc., or when they are caused to react withactive methylene-containing bodies. in either case plastic compositionsare obtained.

In contrast with the protcids the amino acids and their salts arecrysta-lloids, or, if impure, may be obtained in crystalline form bysimple recrystallization processes. They exhibit the properties typicalof crystalloids, for example sharp melting or decompositiontemperatures. In solution, the values of their freezing pointdepressions,

aldehyde-reactable organic amphoteric boiling point elevations andosmotic pressures can be approximated'by simple calculations.

The free amino acids represent the simplegt su stances having nopolypeptide linkages that are known. Theoretically the simplest possibleamino acid would be carbamic acid -or amino formic acid, NHzCOOH, which,however, is not known to exist in a free state. Glycine or amino aceticacid. NHzCHzCOOH, is the simplest amino acid known to exist in a freestate.

It will be noted that such organic amphoteric substances asamino'facids, of which glycine is one of numerous examples, contain bothan acid group, CO0H, and a basic group, NH2. The amphoteric substanceson ionization give simultaneously two ions, one negatively charged andthe other positively charged, leavinga residual molecule with two equaland opposite charges.

It is known that free or uncombined amino acids (hereafter for brevityreferred to merely as "amino acids), for example amino carboxylic acidsand amino sulfonic acids, can react with basic substances such as sodiumand potassium carbonates and hydroxides, trimethyl amine, pyridine,morpholine, aniline, cyclohexyl amine, naphthyl amine, diethanol amineand the like to give the corresponding salts of the amino acid. Thesesalts are basic not because of the added alkali, but because the NH:,group or the amino acid has been freed of the neutralizing effect of the-COOH-group, this group being neutralized by the added base. Thus,sodium glycinate, NHzCHzCOONa, is alkaline in its reactions. Similarly,the original -NH: group of the amino acid can be neutralized by addingacid, such as sulfuric, hydrochloric, acetic, benzoic and the like,resulting in acidic glycine salts. In these salts the COOH group is freeto ionize as an acid, since the influence of the NH: group has beenremoved by the added acid"; Thus, glycine hydrochloride,HCLNHaCHzCOOI-I, is acidic in nature.

It also is known that the amino acids can be caused to react with analdehyde to form alkoylol derivatives. For example, when formaldehydeand glycine are condensed, acidic methylol glycine, HOCHzNHCHzCOOH, isobtained. However, unless the amino nitrogen has at least one hydrogenatom attached directly-thereto the amino acid will not condense with analdehyde or other active methylene-containing body to form an 'alkylolderivaive. The amino acids and their salts used in carrying'the presentinvention into eflect in all cases contain either an unsubstituted NH=group or a partly substituted amino group, that is, an amino groupwherein one and only one of-the amino hydrogens has been replaced by asubstltuent group. Another characteristic of the amphoteric amino acidsis that they can be esteri- It also has been suggested that amino acidssuitable for use as textile assistanw can be prepared by causing toreact (1) an amide of a high molecular weight carboxylic or sulfonicacid containing at least eight carbon atoms and having at least onehydrogen atom directly connected to a nitrogen atom (e. g.,- the amides,monoalkyl amides, cycloalkyl amides and aryl amides of lauric, oleic orstearic acids), (2) formaldehyde or a formaldehyde-yielding substanceand (3) a low molecular weight amino carboxylic or sulfonic acid havingat least one hydrogen atom directly connected to a nitrogen atom (e. g.,sarcosine, taurine, methyl taurine and z-toluidine- 5-sulionic acid) Thepresent inventiomis based on my discovery that new and valuablesynthetic materials can be producedby reaction of ingredients comprisingessentially an amino-triazine (that is, an

aminotriazine containing at least oneactive hydrogen atom in themolecule, specifically in an amino radical'i'th'ereof), an activemethylenecontaining body and an amino acid or a. salt thereof. Examplesof amino acids that maybe employed are the monoamino monocarboxylicacids, e. g., glycine, alanine, aline, norvalinedeucine, -norleucineisoleucine,= valine, isovaline, phenylalanine," tyrosine, serine,alpha-aminobutyric acid, aloha-amino-beta-hydroxybutyric acid. cysteine,methionine, etc.; cystine; the man. oamino-dicarboxylic acids, e. g.,aspartic acid, glutamic acid, etc; the diamino-mcnocarboxylic acids. e.g., arginine. lysine, ornithine, asparagine, citrulline, etc.: theheterocyclic amino acids, e. g., histidine, tryptophane, proline,oxyproline, hydrooxyproline, etc.: the heterogeneous amino acids;

e. g.,the ortho, meta and para amino benzoic acids, beta amino propion cacid, amino sulfonic acids as, for instance, sulfamic acid (sulfaminicacid), NHzSOiOH. 2-toluidine-5-sulfonic acid. beta-aminoethyl sulionicacid, NHzCHzCHzSOzOH, etc. Salts of the amino acids just mentioned byway of illustration may be employed, for instance basic amino saltsre.g., the barium, calcium, strontium. sodium, potassium, lithium, caesiumand rubidium salts, more particularly, the barium, calcium, strontium.sodium, potassium. lithium, caesium and rubidium sulfamates,

which compounds, it will be noted, include sulfamates of the alkalimetals and of the alkalineadipic. maleic, fumaric, cit'raconic, acrylic,polyacrylic, methacrylic, polymethacrylic, atropic, etc. Mixtures of theabove-mentioned amino ac ds and their salts also may be used. When saltsare used I prefer to employ basic amino I salts either alone or admixedwith an amino acid,

since the resulting resins and molding OOIHDOSi-r tions produced fromsuch resins have better time or storage stability characteristics .hanwhen acidic amino salts are employed.

As'is well known, aminoplasts are synthetic resins derived from amino(including imino) or amido (includin imido) compounds, a typical examplebeing urea-formaldehyde resin (references: Modern Plastics, vol. 1'7,No. 2, October, 1939, page 433; Patents 2,142.840-Grosse, 2,142,860-Nowak, 2,142,861-Schuhmann, 2,157,883--Auerasrmss bach et ,al. andairman-mucus). m the production of aminoplasts (it has heretofore beencommon practice in converting such. materials to the insoluble,infusible state to incorporate into the condensation product or into themolding composition a latent or an active (direct) ouring catalyst. Aspointed out more fully hereafter, this technique and the final productshave not-been entirelysatisfactory.

My invention provides potentially reactive (heat-convertible)aminoplasts and molding com positions of the aminotriazine type thatrequire no additional curing accelerator of the admixedcatalyst type, orother curing reactant, in order to obtain technically useful products.Such aminoplasts may be termed self-curing aminoplasts. It was quitesurprising and unexpected to find that'amphoteric amino acids, which areneutral substances, could be intercondensed with aminotriazines andactive methylene-containing I bodies thereby to impart acceleratedcuring char aoteristics to the resultant partial condensation product,particularly in view of the fact that it has generally been believedheretofore that onLv acids or substances evolving acids at moldingtemperatures would accelerate the curing of a heat-curable aminoplast.

curing characteristics, which compositions yield molded articles freefrom imperfections, such as blisters, discolorations, etc. Suchimperfections are due mainly to localized curing that often oc-- curs inresinous materials of the admixed-catalyst type. As the value of themolded article, especially light-,colored"articles, is materiallyinfluenced by its appearance, it is clear that the discovery of anymeans for decreasing or elimi-' nating entirely the production ofimperfectia'rticles thatrnust be scrapped or sold at reduced I price isof great commercial importance.

The resin syrups and molding compositions of I this invention may bestored for long periods of time without material alteration. In markedcontrast the prior heat-convertible aminoplasts obtained by reactionor'an amino-triazine and an active methylene-containing body, moreparticularly those containing direct or active curing catalysts such asacids, for example hydrochloric, ethyl sulfuric, phthalic, chloracetic,phosphoric; etc., lacked time or storage stability. This necessitatedearly use of the material after incorporating the catalyst.

Furthermore, the molding compositions of this invention cure rapidlyunder heat or under heat and pressure and have good plastic flow duringmolding. Hence molded articles of even the most complicated designs canbe produced rapidly and economically. The cured products have good lightstability, excellent water resistance and surface finish and, ingeneral, meet the strength,

hardness and other requirements of the particular servic application.

In carrying the present invention into effect the initial condensationreaction may be carried out at normal or at elevated temperatures, at

atmospheric, sub-atmospheric or super-atmospheric pressure, in thepresence or absence of a condensation catalyst and under alkaline,neutral or acid conditions. Preferably the reaction is started underneutral or alkaline conditions.

' between the components.

Neutral conditions may be established by neutralizing, if necessary,either the mixed components or the individual component. or componentsprior to admixture. Any substance yielding analkaline aqueous solutionmay be used inobtaining alkaline conditions for the initial condensationreaction; In some cases it may be desirable, in order more quickly toinitiate reaction between the starting materials, to 'add a small amountof a suitable organic or inorganic acid. Thereafter the solution istreated to eliminate acetic conditions due to acid or acid salts. Thatis, the mass is neutralized or is made alkalineby adding an alkalinesubstance. The reaction then is caused to proceed further to produce theself-curing amino-plasts of this invention. 4

In obtaining the neutral, alkaline or acid conditions above described Imay use, for example, ammonia, sodium hydroxide or carbonate, calciumhydroxide, methyl amine, diethyl' amine, tri-isopropy1 amine, ethanolamines, tri-isopropanol amine, etc., mixtures of such alkalinesubstances, inorganic or organic acids such as hydrocloric, sulfuric,phosphoric, acetic; acrylic, crotonic, malonic, etc, or acid salts suchas sodium acid sulfate, monosodium phosphate, monosodium phthalate,etc., or mixtures of acids, of acid salts,

or of acids and acid salts.

Various ways may be employed for effecting ethylene glycol monoallnvlethers, etc;

Alternatively, I may add, the amino acid (or'a salt thereof) to apartial condensation product of an aminotriazine and an activemethylenecontaining body and eifect further condensation In producingsuch a partial condensation product I prefer tocause the condensationreaction between the aminotriazine and the active methylene-containingbody to take place inthe presence of a primary condensation catalyst anda secondary condensat-ion catalyst. The primary condensation catalystadvantageously is a member 01' the class con sisting of (1)nitrogen-containing basic tertiary compounds that arealdehyde-non-reactable, e. g., tertiary amines such as trialkyl (e.g.,'trimethy1, triethyl, etc.) amines, 'triaryl (e. g.,' triphenyl,etc.) amines, etc., and (2) nitrogen-containing basic compounds that arealdehyde-reactable, for instance ammonia, primary amines (e. g., e hylamine, propyl amine, etc.) and secondary amines (e. g., dipro yl amine,diethyl amine, etc.) The secondary condensation catalyst, whichordinarlly is used in.an amount less than the amount of primarycatalyst, should be a fixed alkali, for instance a carbonate, cyanide orhydroxide of an alkali metal (e. g., sodium, potassium, lithium,

etc.).

Another method of effecting reaction between the ingredients comprisesfirst partially condense to this condensation product and effect furtherreactionbetween thecomponents.

ti a1 condensation product of an aminotriazine and an activemethylene-containing body and then causing the reaction 'to proceedfurther. Or, I may condense .or partly condense an amino acid or a saltthereof with 9, mol excess of an active methylene-containing body, addan aminotriazine Instead of using a single amino acid or a single saltofan amino acid I may, if desired, use a plurality of differentaminoacids or of different salts of amino acids. Mixtures of one or moreamino acids andone or more salts of amino acids may be caused to reactwith an aminotriazine and an active methylene-containing body as abovede; scribed. Particularly good results are obtained when an amphotericamino acid and a basic salt of such an'acid, in molar ratios to eachother adjusted to give a predetermined pI-I as described more fully inmy copending application Serial No. 256,998, are caused to react with anaminotriazine and an active methylene-containing body.

Still other ways may be ,employedin combining i the components and inproducing the unmodified ing the amino acid (or a, salt thereof) withthe and modified condensation products of this invention, as will bereadily understood by those skilled in the art as the description of theinvention proceeds.

The products obtained as described above properly may be designated asintermediatecondensation products. They are heat-convertible resin- -ousbodies which alone or mixed .with fillers, pigments, dyes, lubricants,plasticizers. etc., may be used, for example, as molding compositions.The modified and unmodified resinous masses are self-convertible underheat or under heat and pressure to the insoluble, ,infusible state.

Depending upon the particular reactants employed and the particularconditions of reaction. .these intermediate condensation products varyfrom clear, colorless, syrupy, water-soluble liquids to viscous milkydispersions and gel-like masses of decreased solubility in ordinarysolvents such as alcohol, glycol. glycerine, water, etc. ese liquidintermediate condensation products may be'concentrated or dilutedfurther by the removal or addition of volatile solvents to form liquidcoating compositions of adjusted viscosity and concentration. The liquidcompositions may be used, for instance, as surface-coating materials. inthe production of paints, varnishes, lacquers, enamels, etc., forgeneral adhesive applications, in producing laminated articles and fornumerous other purposes. The liquid intermediate condensation productsalso may be used directly as casting resins. Those intermediate productsof a gel-like nature may be dried and granulated to form clear,unfilled, heat-convertible resins.

In order that those skilled in the art better may understand how thisinvention may be carried into'eilect, the following examples are givenby wayof illustration. All parts are by weight.

All of the above components with the exception of the glycine were mixedand heated under reflux at the boiling temperature of the mass for 10minutes. The stated amount of glycine was now added and the mixture wasbrought to boiling thereby to cause the glycine to intercondense withthe melamine-formaldehyde partial condensation product. The hot resinoussyrup was mixed with 670 parts alpha cellulose in flock form and 4 partsof a mold lubricant, specifically zinc stearate, to form a molding(moldable) compound.

The wet compound was dried at 67 C. for 2 hours. The dried compound wasmolded for 2 -minutes at 130 C. under a pressure of 2,000

pounds per square inch. The molded pieces could be pulled hot from themold without distortion. They were well cured throughout and were verylight-colored.

Example 2 Parts Melamine 315.0 Urea 1 50.0

Aqueous solution of formaldehyde (approx. 37.1% HCHO) 1000.0 Aqueousammonia (28% NH?) 30.0 Sodiumhydroxide in 30 parts water 0.6

Glycine 10.95

at 75 C. for 1 hours. The dried compound was molded for 2 minutes at 130C. under a pressure of 2,000 pounds per square inch, yieldingwell-curedfmolded pieces that could be pulled hot from the mold withoutdistortion.

Example 3 Parts Melamine Y 315.0 Thiourea 190.0

Aqueous solution of formadehyde (api prox. 3 7.1% HCHO) 1000.0 Aqueousammonia (28% NHa) 30.0 Sodium hydroxide in 30 parts water 0.6 Glycine -11 0.98

The method of making the resin syrup was the same as in Example 1 withthe exception that the initial heating period prior to adding theglycine was 15 minutes as in Example 2. A molding compound was made bymixing the hot resin syrup with 490 parts alpha cellulose and 4 partszinc stearate, followed by drying the wet compound for 2 /2 hours at 70C. The dried compound was molded at 130 C. under a pressure of 2,000pounds per square inch, yielding well-cured molded pieces of goodappearance and excellent resistance to water.

Example 4 Parts Melamine 472.5 Dicyandiamide 105.0 Aqueous solution offormaldehyde (apv prox. 37.1% HCHO) 1200.0 Aqueous. ammonia (28% NR1)";30.0 Sodium hydroxide in 30 parts water"--- 0.6 Glycerine 2.04

. All of the above components with the exception of the glycine wereheated together under reflux at the boiling temperature of the mass for15' minutes, after which the stated amount of glycine was added and themass was brought to boiling temperature. The resulting hot syrup wasmixed with 610 parts alpha cellulose and 4 parts zinc stearate to form amolding composition. The wet compound was dried at room temperatureuntil sufficiently moisture-free for proper molding. The dried compoundwas molded at 140 C. for 5 minutes under a pressure of 2,000 pounds persquare inch. The molde pieces were well cured throughout.

Example 5 Parts Melamine 1200.0 Ethyl acetoacetate 65.0

Aqueous solution of formaldehyde .(ap-

prox. 37.1% HCHO) 2800.0

Aqueous ammonia (28% NHa) 60.0 Sodium hydroxide in 200 parts water 1.6Glycine 4.0

The same procedure was followed in making the resin syrup as describedunder Example 1.

The hot resin syrup was mixed with 1330 parts alpha cellulose and 8parts zinc stearate to form a molding compound. The wet compound wasdried at 67 C. for 2 /2 hours. The dried compound was molded for 2minutes at 130 C. under a pressure of 2,000 pounds per square inch. Themolded pieceswere well cured throughout and slightly yellow in color.

Example 6 I Parts Melamine 1132.0

Diethyl malonate 216.0 Aqueous solution of formaldehyde (approx.

37.1% I-ICHO) 2800.0

.Aqueous ammonia (28% NHzL--- 60.0

Sodium hydroxide in 120 parts water 1.2

Glycine 4.0

The method of. making the resin syrup wasthe same as in Example 1 withthe exception that the initial heating period prior to adding theglycine was 15 minutesas in Example 2. A molding compound was made bymixing the hot resinous syrup with 1330 parts alpha cellulose and 8parts zinc stearate, followed by drying the wet compound at 67 C. .forhours. The dried compound was molded for 2 minutes at C. under apressure of 2,000 pounds per square inch. The molded pieces could bepulled hot from the mold without distortion. They were well curedthroughout and showed goodplastic flow during molding. I 1

Example 7 r Parts Melamine 283.0

Mixture of 21.5 parts monomethylol methyl ethyl ketone, 5.02 partsdimethylol methyl ethyl ketone and 20.8 parts water. total being Aqueoussolution of formaldehyde (approx.

3'7.% HCHO) 700.0

Aqueous ammonia (2.8% NHa) 15.0 Sodium hydroxide in 25 parts water 1.0Glycine 1.9 v

The same procedure was followed in making the resin syrup as describedunder Example 1.

The hot resin syrup was mixed with 360 parts. alpha cellulose and 2.5parts zinc stearate to form a molding compound. The wet compound wasdried at 67 for 2% hours. Moldedarticles were made from the driedcompound by molding portionsthereof for 2 minutes at 130 .C. under apressure of 2,000 pounds per square inch. The

' 6-methyl-2,4-diaminc-1,3,5-triazine,

mold without distortion. They were welLcured throughout and hadexcellent water resistance.

It will be understood, of course by those skilled in the art that myinvention is not limited to the specific components named in the aboveillustrative examples nor to the specific proportions therein given.Thus, instead oi. using melamine any other aminotriazine (amidogentriazine) containing at least one active hydrogen atom in the molecule,specifically in anamino radical thereof, may be employed. I prefer. touse triazines containing either at least. one unsubstituted amidogen(NH:) group or a plurality of partly substituted amidogen groups.Examples of such triazines which may be usedin producing the newsynthetic materials or this invention are ammeline, ammelide,formoguanamine, Z-amino- 1,3,5-triazine and its substitution products;derivatives of melamine, e. g., 2,4,6-trihydrazino- 1,3,5-triazine,melam, melon, 2,4,6-triethyltriamino -1,3,5 triazine, 2,4,6triphenyltriamino- 1,3,5-triazine, etc.; nuclearly substitutedaminotriazines, e. g., 1-cyano-2 amino-4,6-dimethyl- 1,3,5-triazine,2-chloro-4,6-diamino 1,3,5-triazine,

2-alkyl-4- amino-6-hydroxy-l,3,5-triazines (e. 3., 2-methyl-4-amino-6-hydroxy-L3,5-triazine, etc.) 2-aryl-4-amino-G-hydroxy-l,3,5-triazines (e. g., 2-phenyl-4-amino-6-hydroxy-l,3,5-triazine, etc.),2-phenyl-p-oiw-4,6-diamino-1,3,5-triazine; poly-amino triazines whereinthe hydrogen atoms of one or all of the amino groups are partiallysubstituted by other amino groups, e. 3.,2,4-diamino-6-hydrazino-l,3,5-triazine, 2-amino-4j-dihydrazinol,35-triazine, 2,4,6 trihydrazino -l,3,5-triazine, etc.; poly-aminotriazines wherein the hydrogen atoms of one or all or the amino groupsare par-.

tially substituted by other monovalent substituents (e. g., alkyl, aryl,aralkyl, alkaryl, etc.), for

instance 2-amino-4,6-diethylaminoF1,3,5-triazine, 4-amino-2-methylamino6-chloro-l,3,5-triazine, 4-aminc-2,6-diphenylamino-1,3,5-triazine,2,4-diamino-6-phenylamino-1,3,5-triazine, symmetrical trialkyl andtriaryl melamines; the amidogen V 1,2,3-triazines and the amidogen1,2,4-triazines,

specifically the amino (NH-.-) and the carbamyl (-CONHz) and thethiocarbamyl (-CSNI-Iz) 1,2,3- and 1,2,4-triazines. Additional examplesof amidogen 1,3,5-triazines are given below:

Other examples of amidogen triazines are the .amidogen 1,2,3-triazinesand 1,2,4-triazines cormolded pieces oouldbe removed hot from the thepresent invention into effect are amidogen-1,3,5-triazines.

As shown by certain of the examples a part oi. the aminotriazine may bereplaced by urea, thiourea, dicyandiamide or other reactants.Illustrative examples of other reactantsjhat may be substituted for apart or the aminotriazine are the alkyl ureas, selenoureas and'.'thioureas (e. g., methyl, ethyl, etc., ureas, selenqureas andthicureas), aryl ureas, selenoureas and thioureas (e. g., phenyl urea,selenourea and thiourea, unsymmetrical diphenyl urea, selenourea andthiourea, etc.), alkyl aryl ureas, selenoureas and thioureas (e. g.,unsymmetrical methyl phenyl urea, selenoureav and thiourea,unsymmetrical ethyl henyl urea, selenourea and thiourea, etc.),,lrydroxy ureas, selenoureas and thioureas,

ethanol ureas, selenoureas and thioureas, acetyl urea, selenourea andthiourea, benzoyl urea, selenourea and thiourea, allyl urea, selenoureaand thiourea, 2-chlorallyl urea, selenourea and thiourea,di-(phenylsuliamyl) ureas, selenoureas and. thioureas, guanidine,biguanide, aminoguanidine, "malonic diamide,- maleic diamide,

itaconic dlamide, fumaric diamide, succinic diamide, citric triamide,phthalamide, etc.

In producing these new condensation products the choice of the activemethylene-containing body is dependent largely upon economicconsiderations and upon the particular properties v desired in thefinished product. I prefer to use poly-methylol derivatives of urea,

as the active methylene-containing body formaldehyde or compoundsengendering formaldehyde, e. :g., paraformaldehyde, hexamethylenetetramine, etc. For some applications I may use, for instance,acetaldehyde, propionaidehyde, butyraldehyde, acrolein, methacrolein,crotonaldehyde, benzaldehyde, furfural, etc., mixtures thereof, ormixtures of formaldehyde (or compounds engendering formaldehyde) withsuch aldel'wdes. Illustrative examples of other activemethylene-containing bodies that may be'employed are the monoandpoly-(N-carbinol) derivatives, more particularly the monoand thiourea,selenourea and .iminourea, and of substituted ureas, thioureas,selenoureas and iminoureas .(numerous examples of which are given in thepreceding-paragraph), mono= and poly-(N-carbinol) derivatives or amidesof polycarboxylic acids, e. 3., maleic, itaconic, fumaric, malonic,succinic, citric, phthalic, etc., monoand poly- (N-carbinol) derivativesof amidogen triazines such as those mentioned hereinloefore, etc.Particularly good results are obtained with active methylene-containingbodies such as mono-- and responding to the above amidogen1,3,5-triazines. A

The preferred class of triazines used in carrying di-me'thylol urea andthe methylol melamines, e. g., mono-, di-, tri-, tetra-, pentaandhexamethylol melamines. Mixtures of aldehydes and other activemethylene-containing bodies may be employed, e. g., mixtures offormaldehyde and methylol compounds such, for instance, as dimethylolurea and trimethylolmelamine- The ratio of the reactants to each othermay be considerably varied, but, in general, it is desirable to use atleast one mol of an active ,methylene-containing body for each mol ofand/or salt thereof in all cases is at least sui'-' flcient to impartself-curing characteristics to the resin. Ordinarily not exceedingsubstantially the 2,4,6

a basic salt thereof, e. g., an alkali-metal glycinate such as sodiumglycinate, the molar ratios of the amino acid and the salt thereof withrespect to each other being adjusted to give a asvasee predetermined pH.The salt of theamino acid may be separately prepared and incorporatedinto the reaction mass; or it may be formed in situ by adding to thereaction mixture an amino acid and a base in proportions necessary toform the desired "amount of basic amino salt. Similarly, an acidic aminosalt can be produced in situ by adding to the reaction mass an aminoacid and an organic or inorganic acid in the proportions required toyield the desired amount of form of an alkylol derivative, moreparticularly.

a methylol derivative such, for instance, as dimethylol urea,trimethylol melamine, etc., then higher amounts of such activemethylene-containing bodies are used, for example from 3 /2 to 10 ormore mols of such alkylol derivatives for each mol of the aminotriazine.Taking melamine (an aminotriazine containing three unsubstitutedamidogen groups) as illustrative of the aminotriazine, particularly goodresults are obtained with approximately three mols aldehyde, 'e, g.,formaldehyde, for each mol melamine. If the aminotriazine contains onlytwo unsubstituted amidogen groups (or one unsubstituted and two partlysubstituted amidogen groups), then one advantageously may useapproximately two mols aldehyde'foreach mol of an aminotriazine. If the,aminotriazlne contains only one unsubstituted amidogen group (or twopartly substituted amidogen groups), then no particular-advantage woodproducts, formalized cellulose derivatives. lignin, protein-aldehydecondensation products, aminodiazineand aminodiazole-aldehydecondensation products, phenol-aldehyde condensation products,urea-aldehyde condensation products, aniline-aldehyde condensationproducts, furfural condensation products, modified or unmodified,saturated or unsaturated polyhydric alcoholpolybasic acid condensationproducts, sulfonamide-aldehyde resins, water-soluble cellulosederivatives, natural gums and resins such as shellac, rosin, etc.polyvinyl compounds such as polyvinyl alcohol,-polyvinyl acetate,polyvinyl acetals, specifically polyvinyl formal, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and variousfillers (e. g., wood fl ur. glass fibers, asbestos, including defibratedasbestos, mineral wool, mica, cloth cuttin s. etc.) may be compoundedwith the resin in accordance with conventional practice to providemolding compositions best fitted to yield molded articles of optimumproperties for the particular service application.

The molding compositions of this invention. may be molded .into avariety of shapes under heat and pressure, more particularly attemperatures of the order of 100' to 200 C., preferably from 120 to 180C. Molding pressures may be varied considerably, but usually .are'with-Q in the range of 1,000 to 10,000 pounds per square inch, moreparticularly from 2,000 to 4,000 or 5,000 pounds per square inch,

From the foregoing description it will be seen that the presentinvention provides new and useful compositions of matter comprising acondensation product (in heat-curable or heat-cured state) ofingredients comprising essentially an aminotriazine (amidogen triazine)e. g., melamine, an active methylene-containing body (e. g.,formaldehyde, dimethylol urea, etc.) and an-amino compound selected fromthe class consisting of amphoteric amino acids? (e. g., amphotericamino" carboxylic acids, amphoteric amino sulfonic acids, etc.), saltsthereof and mixtures of amphoteric amino acids and salts thereof. Thescope of the invention also includes' method features for the productionof such condensation products. Foxinstance, one

usually accrues from using much inexcess of one' mol aldehyde for eachmol of such an aminotriazine.

The properties of the fundamental resins of a this invention may bevaried widely by introducing other modifying bodies before, during orafter efiectingcondensation between the primary components.. Thus, 'asmodifying agents I may use, for instance, monohydric alcohols such asethyl, propyl, isopropyl, butyl, amyl, eta, alcohols; polyhydricalcohols such as ethylene glycol, diethylene glycol, glycerine,pentaerythritol, etc.; amides such as formainide, acetamide, stearamide, acryloamide, benzamides, toluene sulfonamides, benzenedisulfonamides, benzene trisulfonamides, adipic diamide, phthalamide,etc.; amines such as ethylene diamine, aniline,

method feature of the invention comprises effectlng partial reactionbetween ingredients comprising an aminotriazinaspecifically melamine andan active methylene-containing body (or ingredients comprising a urea,specifically NHzCONHr, an aminotriazine and an activemethylene-containing body), in thepresence of an alkaline condensationcatalyst, specifically a condensation catalyst comprising ammonia and afixed alkali, adding a small amount of an amphoteric amino acid,specifically glycine, to the resulting partial 'condensation'product andcausing the amphoteric amino acid to intercondense with the saidpartial. condensation product.

Other method features of the invention include, for example, the methodwhich comprises re acting the reaction product of formaldehyde and asalt of sulfamic acid, e. g., calcium sulfamate.

calcium sulfamate, the said derivative having been prepared by reactingformaldehyde with said salt under alkaline conditions; the method I Theyalso may be used in the such, for

v or other aminotriazine, formaldehyde and asulfamate, e.,'g., asulfamateof an alkaline-earth metal; the method which compriseseffecting reaction under heat between ingredients including (1) anaminotriazine, e. g., melamine, and (2) the product of reaction, underalkaline conditions, of formaldehyde and a sulfamate, specifically asulfamate of an alkaline-earth metal as, for instance, calciumsulfamate, and the products obtained by practicing such methods. Myinvention also provides thermosetting (heathardenable) moldingcompositions comprising a filler, e. g.-, a cellulosic filler, and aheat-curable condensation product of this invention, e. 8., aheat-hardenable (heat-curable) condensation product of ingredientscomprising melamine (or urea and melamine),

compound of the class herein'described, e. g

, glycine, an alkali-metal salt of glycine such, for

The modified and unmodified resinous compositions of this invention havea wide variety of uses. For example, in addition to their use in theproduction of molding compositions, they may be used as laminatingvarnishes in the production of laminated articles wherein sheetmaterials, e. g., paper, cloth, sheet asbestos, etc., are coated andimpregnated with the resin, superimposed, and thereafter united underheat and pressure. production or wire or baking enamels, for bonding orcementing together mica flakes to form a laminated mica. article, forbonding together abrasive grains in the production of resin-bondedabrasive articles instance, as grindstone, sandpapers, especially thoseintended for wet-sanding Operations, in the manufacture of electricalresistors,

(1), and (3) mixtures of (a) the acids of (1) with (b) salts of theacids of (1).

3. A composition as in claim 1 wherein the active methylen -,containingbady is formaldehyde.

4. A composition as in claim 1 wherein the aminotriazine is melamine.

formaldehyde or com pounds engendering formaldehyde and an amino 5. Aheat-curable resinous condensation product of ingredients comprising anaminotriazine, formaldehyde and an amino compound selected from theclass consisting pf (l) amphoteric amino carboxylic acids and amphotericamino sulfonic acids, (2) salts of the acids of (1), and (3) mixtures of(a) the acids of (1) with (b) salts of theacids'of(1).- 1

6. A product comprising,the heat-cured resinous condensation product ofclaim 5. v

"I. A heat-curable resinous composition comprising a soluble, fusiblecondensation product of ingredients comprising the following componentsin the stated molar ratios: 1 mol of an aminotriazine from 1 to 3% molsformaldehyde and not exceeding substantially.0.3 mol'of an aminocompound selected from the class consisting of (1) amphoteric aminocarboxylic acids and amphoteric amino sulfonic acids, (2) salts of theacids of (1), and (3) mixtures of-(a) the acids of (1) with (b) salts ofthe acids of 1) 8. A product comprising the cured resinouscomposition-of claim 7.

9. A composition comprising the reaction prod-- uct of ingredientscomprising an aminotriazine, an active methylene-containing body and anamphoteric amino carboxylic acid. v

10. Acomposition comprising the reaction product of ingredientscomprising an aminotriazine, an active methylene-containing body and anamphoteric amino suli'onic acid.

'11. A- heat-curable resinous not of ingredients comprising urea,melamine, formaldehyde and glycine;

12. A product comprising the heat-cured resinous condensation product ofclaim 11.

13. A composition comprising the product of F reaction of (1) a partialcondensation product obtained by reaction, while admixedwith an alkalinesubstance, of ingredients comprising an etc'. They also may be used asfire retardants densation product of ingredients comprising anaminotriazine, an active methylene-containing body and an amino compoundselected from the class consisting of (1) amphoteric amino carboxylicacids and amphoteric amino sulfonic acids, 2) salts of the acids of (1),and (3) mixtures 'of (a) the acids of (1) with (b) salts of the acids of(1),.

2. A composition of matter comprising an alcohol-modified condensationproduct of ingredients comprising an aminotriazine, an activemethylene-containing body and an amino compound selected from the classconsisting of (1) amphoteric-amino carboxylic acids and amphoteric aminosulfonic acids, (2) salts of the acids of 1 metal salt of glycine withrespect to each other I aminotriazine and formaldehyde and (2) anaminocompound selected from the class consisting of 1) amphoteric aminocarboxylic acids and vamphoteric amino sulfonic acids. (2) salts of theacids of- (1'), and (3) mixtures of (a) the acids of (i) with (b) saltsof the acids of (1).

14. A composition comprising the product of reaction of ingredientscomprising melamine, for maldehyde, glycine and an alkali-metal salt ofglycine, the mol ratio of glycine and the alkalibeing adjusted to give apredetermined pH.

15. A thermosetting molding composition comprising a. filler and aheat-hardenable condensation product of ingredients comprising anaminotriazine, formaldehyde and an amino compound selected from theclass consisting of (1) amphoteric amino carboxylic acids and amphotericamino sulfonic acids, (2) salts of the acids of (1), and (3) mixtures of(a) the acids of (1) with (b) salts of theacids of (1).

. 16. A product comprising the heat-hardened molding composition ofclaim 15.

17. The method of preparing new condensation products which comprisesefiecting reaction between ingredients comprising essentially anaminotriazine, an active methylene-containing body and an amino compoundselected from the condensation prod class consisting boxylic acids andamphoteric amino sulfonic acids, (2) salts of tures of (a) the acids of(1) with (b) salts of the acids of (l) 18. The method which compriseseffecting par tial reaction between melamine, urea and formaldehyde inthe presence and a fixed alkali, glycine to the resulting partialcondensation product and causing with the said partial condensationproduct- 19. A composition of matter comprising the condensation productof an maldehyde and glycine.

20. A composition of condensation product of melamine, formaldehyde,glycine and a salt of glycine.

21. A.resinous composition tion'of ingredients comprising anaminotriazine, formaldehyde and glycine, said reaction being effectedwhile the said components are admixed with an alkaline substance. i 22.Acomposition comprising uct of reaction of a a partial condensationproduct obtained by reaction of ingredientscomprising melamine andformaldehyde whilzadmixed with a small amount and a fixed alkali.

23'. The method which comprises reacting the reaction product offormaldehyde and a salt of suliamic acid with melamine, said reactionbeing effected by the application of heat.

24. The method which reaction product of formaldehyde and calcium Patentlio 2 5775868 sulfamate with melamine, said reaction being effected bythe application of heat.

25. The product produced by reacting melamine with .the reaction productof formaldehyde and calcium sulfamate, said reaction being eifected bythe application of heat.

26. The method which comprises bringinginto contact at reactiontemperature melamine and a formaldehyde derivative of a sulfamic acidsalt, said derivative having been prepared by reacting formaldehyde withsaid salt under alkaline conditions.

27. The method Which'comprises bringing into contact at reactiontemperature melamine and a formaldehyde derivative of calcium sulfamate,said derivative having been prepared by reacting formaldehyde with saidsulfamate under alkaline conditions.

28. The method which comprises bringing into contact at reactiontemperature ingredients including melamine, formaldehyde and a sulfamateof an alkaline-earth metal.

29. The product obtained by effecting reaction under heat betweeningredients including (1) melamine and (2) the reaction product offormaldehyde and a sulfamate.

30. The method which comprises effecting reaction under heat betweeningredients including (1) melamine and (2) the product of reaction,under alkaline conditions, of formaldehyde anda sulfamate of analkaline-earth metal.

31. The product obtainedby effecting reaction under heat betweeningredients including (1) melamine and (2) the product of reaction,under alkaline conditions, of formaldehyde. and a sulfamate of analkaline-earth metal.

- GAETANO F. DALELIO.

of (1) amphoteric amino carthe acids of (1), and (3) mixingredientscomprising a condensation catalyst comprising ammonia adding a smallamount of the glycine to intercondense aminotriazine, formattercomprising the obtained by reacthe resinous prodglycine with smallamount of a condensation catalyst comprising ammonia 3? comprisesreacting the d CERTIFICATE OF CORRECTION. v

1 June 12, 1915. GAETANO F. D'ALELIO.

in the printed specification of the above numbered patent requiringcorrection as follows": Page 1, secline M4, for "alkoyl ol" read--alkylol--; line 5 2,' f0r' "derivaive" read -derivat ive-; page 5,first column, line 12, for "acetic" acidic-; line 25, for hydrocloric"read hydroch1or1c--;

column,

It is hereby certified that error appears 0nd column,

IBad. page LL, first line .71, for "Glycerine" read "Glycineand secondcolumn, line page 5, first column, line 11., after "course" insert acomma; page 6, 'first column, line 66, for "acryloamide" road page 7,first column, li.ne -h5, for :"gr1ndstone' read grindstonesand that thesaid Letters Patent should be read with thiscorrection therein thatthefsame may conform to the record of the case in the Patent Office.

si ned and sealed this 9th day of October, A- D. 1915.

--acrylamlde Leslie Frazer (Seal) First Assistant Commissioner ofPatents.

class consisting boxylic acids and amphoteric amino sulfonic acids, (2)salts of tures of (a) the acids of (1) with (b) salts of the acids of(l) 18. The method which comprises effecting par tial reaction betweenmelamine, urea and formaldehyde in the presence and a fixed alkali,glycine to the resulting partial condensation product and causing withthe said partial condensation product- 19. A composition of mattercomprising the condensation product of an maldehyde and glycine.

20. A composition of condensation product of melamine, formaldehyde,glycine and a salt of glycine.

21. A.resinous composition tion'of ingredients comprising anaminotriazine, formaldehyde and glycine, said reaction being effectedwhile the said components are admixed with an alkaline substance. i 22.Acomposition comprising uct of reaction of a a partial condensationproduct obtained by reaction of ingredientscomprising melamine andformaldehyde whilzadmixed with a small amount and a fixed alkali.

23'. The method which comprises reacting the reaction product offormaldehyde and a salt of suliamic acid with melamine, said reactionbeing effected by the application of heat.

24. The method which reaction product of formaldehyde and calcium Patentlio 2 5775868 sulfamate with melamine, said reaction being effected bythe application of heat.

25. The product produced by reacting melamine with .the reaction productof formaldehyde and calcium sulfamate, said reaction being eifected bythe application of heat.

26. The method which comprises bringinginto contact at reactiontemperature melamine and a formaldehyde derivative of a sulfamic acidsalt, said derivative having been prepared by reacting formaldehyde withsaid salt under alkaline conditions.

27. The method Which'comprises bringing into contact at reactiontemperature melamine and a formaldehyde derivative of calcium sulfamate,said derivative having been prepared by reacting formaldehyde with saidsulfamate under alkaline conditions.

28. The method which comprises bringing into contact at reactiontemperature ingredients including melamine, formaldehyde and a sulfamateof an alkaline-earth metal.

29. The product obtained by effecting reaction under heat betweeningredients including (1) melamine and (2) the reaction product offormaldehyde and a sulfamate.

30. The method which comprises effecting reaction under heat betweeningredients including (1) melamine and (2) the product of reaction,under alkaline conditions, of formaldehyde anda sulfamate of analkaline-earth metal.

31. The product obtainedby effecting reaction under heat betweeningredients including (1) melamine and (2) the product of reaction,under alkaline conditions, of formaldehyde. and a sulfamate of analkaline-earth metal.

- GAETANO F. DALELIO.

of (1) amphoteric amino carthe acids of (1), and (3) mixingredientscomprising a condensation catalyst comprising ammonia adding a smallamount of the glycine to intercondense aminotriazine, formattercomprising the obtained by reacthe resinous prodglycine with smallamount of a condensation catalyst comprising ammonia 3? comprisesreacting the d CERTIFICATE OF CORRECTION. v

1 June 12, 1915. GAETANO F. D'ALELIO.

in the printed specification of the above numbered patent requiringcorrection as follows": Page 1, secline M4, for "alkoyl ol" read--alkylol--; line 5 2,' f0r' "derivaive" read -derivat ive-; page 5,first column, line 12, for "acetic" acidic-; line 25, for hydrocloric"read hydroch1or1c--;

column,

It is hereby certified that error appears 0nd column,

IBad. page LL, first line .71, for "Glycerine" read "Glycineand secondcolumn, line page 5, first column, line 11., after "course" insert acomma; page 6, 'first column, line 66, for "acryloamide" road page 7,first column, li.ne -h5, for :"gr1ndstone' read grindstonesand that thesaid Letters Patent should be read with thiscorrection therein thatthefsame may conform to the record of the case in the Patent Office.

si ned and sealed this 9th day of October, A- D. 1915.

--acrylamlde Leslie Frazer (Seal) First Assistant Commissioner ofPatents.

